CN114907610B - Preparation method of porous polymer microsphere oil removal resin - Google Patents

Preparation method of porous polymer microsphere oil removal resin Download PDF

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CN114907610B
CN114907610B CN202210702328.2A CN202210702328A CN114907610B CN 114907610 B CN114907610 B CN 114907610B CN 202210702328 A CN202210702328 A CN 202210702328A CN 114907610 B CN114907610 B CN 114907610B
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pore
resin
dosage
solution
monomer
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CN114907610A (en
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曹敏
孙宁磊
付国燕
李勇
林洁媛
李诺
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China ENFI Engineering Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene

Abstract

The invention relates to the technical field of functional polymer materials, and discloses a preparation method of porous polymer microsphere oil removal resin. The porous polymer microsphere degreasing resin is prepared by mixing and adding a monomer, an initiator and a pore-forming agent into a dispersing agent solution to carry out suspension polymerization; wherein the monomers are styrene and divinylbenzene; the pore-forming agent is formed by mixing at least two of liquid paraffin, ethyl acetate, isobutyl acetate, toluene and silicone oil; the dosage of the pore-forming agent is 80-120 wt% of the dosage of the monomer. The reaction process is simple and quick, the prepared oil removal resin has a nano-pore structure, the pore diameter and the specific surface area are proper, the oil absorption rate of the finished product is high, and the use requirement is met.

Description

Preparation method of porous polymer microsphere oil removal resin
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a preparation method of porous polymer microsphere oil removal resin.
Background
As one of the functional polymer materials, macroporous resin is an organic polymer adsorbent with better adsorption performance developed at the end of the 70 th century, has a three-dimensional space stereo pore structure inside, has larger pore diameter and specific surface area, is insoluble in organic solvents such as acid, alkali, ethanol, acetone, hydrocarbon and the like, and is stable to oxygen, heat and chemical reagents. Macroporous adsorption resins generally do not have ion exchange groups, but the interior of the beads is provided with adsorption sites and diffusion channels matched with the molecular size of the separation object, and the particles are usually white spherical particles and are generally classified into nonpolar and polar two types according to the molecular structure of chain links.
The pore-forming technology of the synthetic macroporous adsorption resin comprises polymerization pore-forming, friedel-Crafts crosslinking pore-forming (namely post-crosslinking pore-forming), emulsion pore-forming, ultrafine powder pore-forming and the like. The macroporous adsorption resin has wide application in the fields of wastewater treatment, pharmaceutical industry, chemical industry, analytical chemistry, clinical identification and the like.
Chinese patent CN103275258A discloses a preparation method of porous adsorption resin, which is prepared from a single polymer porous resin, and the adsorption capacity is only about 23% and less although the specific surface area is large and the adsorption selectivity is strong.
Chinese patent CN104829765B discloses a microporous ionized high rarity resin, which has a pore size of 50 μm to 100 μm although the specific surface area is high.
In summary, the inventors herein have recognized that the current prior art for preparing macroporous adsorbent resins has at least the following problems: the formula is complex; the number of micropores is small, and the oil absorption multiplying power is low; the contradiction between the aperture and the specific surface area is difficult to meet the requirements of the market on the high-performance oil-absorbing resin material, and the like.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of porous polymer microsphere degreasing resin, so as to obtain porous degreasing resin with high oil absorption rate and strong adsorptivity, and solve the problems of the existing porous adsorption resin and preparation process.
The above object can be achieved by the following embodiments of the present invention:
the invention provides a preparation method of porous polymer microsphere oil removal resin, which comprises the following steps: the porous polymer microsphere degreasing resin is prepared by mixing and adding a monomer, an initiator and a pore-forming agent into a dispersing agent solution for suspension polymerization; wherein the monomers are styrene and divinylbenzene; the pore-forming agent is formed by mixing at least two of liquid paraffin, ethyl acetate, isobutyl acetate, toluene and silicone oil; the pore-forming agent is used in an amount of 80wt.% to 120wt.% of the monomer.
Optionally, the pore-forming agent at least comprises liquid paraffin.
Optionally, the preparation method comprises the following steps:
step S10, dissolving a dispersing agent to obtain a dispersing agent solution; mixing and stirring an initiator, a monomer and a pore-forming agent to obtain a mixed solution;
step S20, adding the mixed solution into the dispersing agent solution, stirring for 30-1 h, wherein the stirring speed is 120-250 r/min, carrying out suspension polymerization at 60-85 ℃ for 1-2 h, and preserving heat at 90-100 ℃ for 2.5-5 h;
step S30, filtering the solution while the solution is hot, washing with hot water, and drying to obtain granular particle resin;
and S40, cleaning the granular particle resin by using toluene or acetone, and drying for 22-26 hours to obtain the porous polymer microsphere degreasing resin. The porous polymer microsphere degreasing resin has permanent macropores.
Optionally, in step S30, the temperature of the hot water is 60-80 ℃, and the dosage is 3-5 times of the solution quantity; the drying temperature is 80-110 ℃ and the drying time is 22-26 h. For example 24h.
Optionally, before step S40, the method further includes: introducing phenolic hydroxyl groups into the granular particles for repolymerization to obtain the high-adsorption resin, wherein the reaction temperature is 65-80 ℃ during repolymerization, and the reaction time is 3-6 h.
Optionally, the amount of divinylbenzene in the monomer is between 14.3% and 33.2%.
Optionally, the dispersant is polyvinyl alcohol.
Optionally, the dispersant is used in an amount of 0.05wt.% to 0.2wt.% of the monomer.
Optionally, the initiator is one or two of Benzoyl Peroxide (BPO), azodiisobutyronitrile and lauroyl peroxide.
Optionally, the initiator is used in an amount of 1wt.% to 4wt.% of the monomer.
The porous polymer microsphere degreasing resin has a nano-pore structure, and the specific surface area of the resin is 18m 3 /g～72m 3 And/g, the oil absorption rate of the finished product is 12 g/g-22 g/g.
The beneficial effects are that: the preparation method is simple and quick in reaction process, the prepared oil removal resin is of a nano-pore structure and large in specific surface area, the oil absorption rate of a finished product is high, the use requirement is met, the contradiction between the pore diameter and the specific surface area is solved, and the copolymer with proper pore diameter and specific surface area is obtained.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As described in the background art, the inventor of the present application recognizes that the porous resin prepared by the prior art has a large specific surface area and a strong adsorption selectivity, but has a small adsorption amount in some documents, and the porous resin has a large pore volume and a small specific surface area and a high adsorption amount in other documents, but has a weak adsorption strength, so that the specific surface area and the pore diameter of the porous resin in the prior art are contradictory, and the high adsorption amount and the strong adsorption of the porous resin cannot be achieved at the same time; based on the method, the preparation process is improved, so that the prepared porous microsphere oil-absorbing resin not only has a large number of uniformly distributed nano-pore structures, but also has a large specific surface area, the oil adsorption capacity is improved, and the oil removal effect is good.
The preparation method of the porous polymer microsphere degreasing resin provided by the invention comprises the steps of mixing a monomer, an initiator and a pore-forming agent formed by mixing, and then adding the mixture into a dispersing agent solution for suspension polymerization reaction, so that the porous polymer microsphere degreasing resin is prepared. The porous resin prepared by stirring and mixing the mixed pore-forming agent, the monomer and the initiator and then adding the mixture into a dispersing agent solution for suspension polymerization reaction has a large number of uniformly distributed nano pore structures, the pore diameter and the specific surface area are proper, the oil absorption rate of a finished product is high, and the preparation process is simple and quick.
The porous polymer microsphere degreasing resin provided by the embodiment of the invention is prepared by suspension polymerization, and comprises the following raw materials in parts by weight: 100 parts of monomer; 1-4 parts of an initiator; 80-12 parts of pore-forming agent; 0.05 to 0.2 part of dispersing agent. Further, styrene and divinylbenzene are used as monomers, at least two of liquid paraffin, ethyl acetate, isobutyl acetate, toluene and silicone oil are mixed to be used as a mixed pore-forming agent, one or two of Benzoyl Peroxide (BPO), azodiisobutyronitrile and lauroyl peroxide are used as an initiator, polyvinyl alcohol is used as a dispersing agent, and the spherical porous oil-absorbing resin with a nano pore structure is prepared through suspension polymerization by improving the process and the proportion, and the spherical porous oil-absorbing resin has high specific surface area and high oil absorption rate of finished products. The proper pore-forming agent, cross-linking agent, initiator and the proportion thereof solve the contradiction between the pore diameter and the specific surface area, thereby obtaining the copolymer with proper pore diameter and specific surface area.
The porous polymer microsphere degreasing resin and the preparation method thereof are further described below by combining an embodiment, and the preparation method comprises the following steps:
and step S10, dissolving the dispersing agent to obtain a dispersing agent solution. Mixing and stirring the initiator, the monomer and the pore-forming agent to obtain a mixed solution. In view of the difficulty in dissolving the dispersant, a dispersant solution is prepared and then mixed in order to improve the preparation efficiency.
Preparing a dispersant solution: setting up a three-neck flask with a nitrogen protection device in a constant-temperature water bath kettle with the water bath temperature of 60-70 ℃ and preferably 65 ℃, adding the dispersing agent polyvinyl alcohol and deionized water, wherein the dispersing agent is 0.05-0.2 wt% of the monomer, and stirring to completely dissolve the dispersing agent to obtain a dispersing agent solution. By adopting the polyvinyl alcohol as the dispersing agent, coalescence among early liquid drops and among middle and later polymer particles can be prevented in the polymerization reaction process, and the particle characteristics of granularity, granularity distribution, particle morphology and the like of the suspension polymer are controlled by controlling the dosage of the dispersing agent, so that the oil absorption effect of the porous polymer microsphere oil removal resin is improved.
Preparing a mixed solution: mixing and stirring the initiator, the monomer and the pore-forming agent to obtain a mixed solution.
The monomers are styrene and Divinylbenzene (DVB), and further, the dosage of the divinylbenzene in the monomers is 18.3-28.2 percent, and the monomers are styrene and divinylbenzene from which polymerization inhibitors are removed. The styrene and the divinylbenzene are mixed with an initiator and a pore-forming agent for polymerization reaction, and the dosage is optimized, so that the porous polymer microsphere degreasing resin with excellent mechanical properties and good oil absorption effect is obtained.
Further, the method for removing the polymerization inhibitor is to wash with sodium hydroxide, dry with anhydrous calcium chloride and store at low temperature. Specifically, the washing is repeatedly performed by using 5% NaOH aqueous solution, and then anhydrous CaCl is used 2 Drying, and storing in refrigerator at 0-3 deg.c. Compared with the prior art, the polymerization inhibitor removing method does not need to increase filter column equipment, does not need to carry out operations such as reduced pressure distillation and the like, only uses NaOH for washing, and does not contain water CaCl 2 Drying is carried out, the treatment steps are simple, the operation is convenient, and the polymerization inhibitor removal effect is improved, so that the polymerization reaction is convenient to carry out, and the porous polymer microsphere has excellent mechanical property and oil absorption effect.
The initiator is one or two of Benzoyl Peroxide (BPO), azodiisobutyronitrile and lauroyl peroxide; the amount of the initiator is 1wt.% to 4wt.% of the amount of the monomer. The molecular weight of the high polymer is controlled by controlling the usage amount of the initiator, the net structure of the copolymer and the release speed of the polymerization heat are controlled, and the polymerization phenomenon is caused by controlling the usage amount to reduce, so that the polymerization reaction is facilitated, and the mechanical property and the oil absorption effect of the porous high polymer microsphere are ensured.
The pore-foaming agent is formed by mixing at least two of liquid paraffin, ethyl acetate, isobutyl acetate, toluene and silicone oil, the dosage of the pore-foaming agent is 80-120 wt.% of the dosage of the monomer, and the structure and the performance of the copolymer are changed by adopting the pore-foaming agents with different properties to mix and control the dosage, so that the porous polymer microsphere oil removal resin has a large specific surface area and a proper pore diameter. The inventor finds that the solvating capability of the polymer is the addition of the solvating capability of each component according to the proportion of the components by taking two or more mixed solvents as the pore-forming agents, the pore-forming agents with different properties have very obvious influence on the pore structure and the performance of the porous resin prepared by suspension copolymerization, the influence is mainly due to the interaction between the pore-forming agents and the copolymer, the smaller the thermodynamic affinity of the pore-forming agents to the copolymer is, the larger the porosity of the copolymer is, and the pore structure has a certain relationship with the second linear coefficient capable of reflecting the interaction between the polymer and the solvent.
Preferably, the porogen comprises at least liquid paraffin. Further, the liquid paraffin accounts for 40-80% of the pore-forming agent. For example, the pore-forming agent is formed by mixing liquid paraffin with toluene or ethyl acetate, and the ratio of the paraffin to the toluene/ethyl acetate is 3:1,3:2,3:3,3:4 and the like. By mixing liquid paraffin with other pore-forming agents and controlling the duty ratio of the liquid paraffin, the pore-forming effect of the pore-forming agents is adjusted, the pore-forming rate is improved, the specific surface area of the porous polymer microsphere degreasing resin is increased, the adsorption performance of the porous polymer microsphere degreasing resin is improved, and the preparation process is simpler and more convenient.
And step S20, adding the mixed solution into the dispersing agent solution, stirring for 30-1 h at the stirring speed of 120-250 r/min, performing suspension polymerization at 60-85 ℃ for 1-2 h, and preserving heat at 90-100 ℃ for 2.5-5 h. Under the implementation mode, suspension polymerization reaction is facilitated, the mechanical property of the microsphere oil removal resin is improved, the microsphere oil removal resin has proper particle size and large specific surface area, and further the oil absorption efficiency is improved. In this step, the resin particle size is controlled by controlling the stirring speed. In the process of realizing the embodiment of the invention, the inventor finds that if the particle size is smaller than 120r/min, the particle size is too large, if the particle size is larger than 250r/min, when the stirring speed is controlled to be 120 r/min-250 r/min, the obtained resin particle size is uniform, the size is moderate, and the optimal adsorption effect is achieved.
And step S30, filtering the solution while the solution is hot, washing with hot water, and drying to obtain the milky or yellowish granular resin. Wherein the temperature of the hot water is 60-80 ℃, and the dosage is 3-5 times of the solution quantity; the drying temperature is 80-110 ℃, and the drying time is 22-26 hours, for example 24 hours. In the step, the tiny polymers adhered on the surfaces of the resin and the surfaces of the micropores and other substances capable of blocking the micropores can be effectively removed by adopting hot water washing, so that the adsorptivity of the porous polymer microsphere degreasing resin is ensured.
And S40, cleaning the granular particle resin by using toluene or acetone, and drying for 22-26 hours to obtain the porous polymer microsphere oil removal resin, namely the polystyrene microsphere, wherein the polystyrene microsphere has permanent macropores and has the aperture of 2-50 nm. In the embodiment, the granular particle resin is further cleaned by adopting acetone or toluene and the like, so that superfluous grease and organic matters on the surface and gaps of the resin ball are thoroughly eluted, and pore-forming agents such as liquid paraffin and the like after the reaction are washed away, thereby ensuring the oil absorption capability of the resin.
In an alternative embodiment, polar groups may also be introduced in order to further increase the oil adsorption capacity of the microsphere degreasing resin. Specifically, before step S40, the method further includes: repolymerization is carried out with compounds/polymers containing phenolic hydroxyl groups to obtain high-adsorption resins. Further, the reaction temperature is 65-80 ℃ and the reaction time is 3-6 h during the repolymerization, so as to ensure the repolymerization. The polar groups are added on the polymer skeleton by introducing phenolic hydroxyl groups for repolymerization, so that the oil adsorption capacity of the resin is further improved. It should be noted that, in this alternative embodiment of the present invention, the prepared resin is further optimized, and the phenolic hydroxyl groups are introduced to perform repolymerization, so that the polar groups are added to the polymer skeleton, which not only has the advantages of the prepared resin, such as a large number of uniformly distributed nano-pore structures, a relatively high specific surface area, and a plurality of phenolic hydroxyl groups, thereby further improving the adsorption capacity of the porous polymer microsphere degreasing resin, and greatly improving the degreasing effect of the porous polymer microsphere degreasing resin. The phenolic hydroxyl group-containing compound/polymer may be, for example, phenol, phloroglucinol, resorcinol, vegetable tannins, urushiol, and the like, and may be used in an amount of 0.3wt.% to 5wt.% of the monomer. The phenolic hydroxyl group-containing microsphere oil removal resin with better performances can be obtained by adopting the phenolic hydroxyl group-containing substance and the dosage, and if the dosage is out of the range, the effect is poor. In some embodiments, the oil absorption rate of the finished product of the finally prepared microsphere oil removal resin can be improved by about 10% -20% by introducing the polar groups.
In the embodiment of the invention, styrene and divinylbenzene with polymerization inhibitors removed are taken as polymer monomers, proper dispersing agents and initiators are selected, the raw material proportion is optimized, a mixed pore-forming agent is adopted, the pore-forming agent, the monomers and the initiators are stirred and mixed and then added into a dispersing agent solution for suspension polymerization, conditions, parameters and the like in each step are improved and optimized, and the porous polymer microsphere degreasing resin is prepared into a nano pore structure with the specific surface area of 18m 3 /g～72m 3 And/g, the oil absorption rate of the finished product is 12 g/g-22 g/g, and the preparation method has the advantages of low preparation cost, simple process and rapidness. The porous polymer microsphere degreasing resin has extremely strong adsorption force on phenol and aromatic substances, such as cresol, phenol and the like.
The following advantages are also provided in some embodiments of the present invention over the prior art: 1) The mixed pore-forming agent and reasonable proportion are adopted, so that the porosity is improved, and the specific surface area of the resin is increased. 2) And the dispersant, the initiator and the monomer which are properly metered are adopted, so that the raw materials are low in cost, and the obtained oil-absorbing resin product is excellent in performance. 3) The resin is cleaned by acetone and the like, and superfluous grease and organic matters on the surface and gaps of the resin ball are eluted, so that the oil absorption capacity of the resin is improved. 4) The phenolic hydroxyl-containing polymer is introduced for repolymerization, so that polar groups are added on the polymer skeleton, and the oil adsorption capacity of the polymer is improved.
Some of the technical solutions in the above embodiments of the present invention are further described below with reference to specific examples, but not limited thereto:
preparation methods of examples and comparative examples:
weighing the raw materials according to the proportion; dissolving a dispersing agent at 65 ℃ to obtain a dispersing agent solution; uniformly stirring the monomer, the pore-forming agent and the initiator to obtain a mixed solution; adding the mixed solution into the dispersing agent solution, controlling the stirring speed, stirring for 30min, carrying out suspension polymerization at 70 ℃ for 1.5h, and preserving heat at 95 ℃ for 3h; filtering the solution while the solution is hot, fully washing the solution with hot water at 60 ℃ with the dosage being 4 times of the solution amount, and drying the solution at 100 ℃ for 24 hours to obtain milky white or yellowish granular particles; and (3) cleaning by using toluene or acetone, and drying for 24 hours to obtain the polystyrene microsphere.
Example 1
Styrene and divinylbenzene are used as monomers (DVB dosage is 14.3%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/toluene: 3:2), BPO is used as an initiator (content is 1.2%), polyvinyl alcohol is used as a dispersing agent (content is 0.14%), and a suspension copolymerization method is adopted to prepare the macroporous crosslinked polystyrene microsphere, wherein the stirring rotating speed is controlled at about 180 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 35m 3 The oil absorption rate per gram can reach 16g/g.
Example 2
Styrene and divinylbenzene are used as monomers (DVB dosage is 24.3%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/toluene: 3:2)), BPO is used as an initiator (content is 1.2%), and polyvinyl alcohol is used as a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 180 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 66m 3 The oil absorption rate per gram can reach 21g/g.
Example 3
Styrene and divinylbenzene are used as monomers (DVB dosage is 23%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/toluene: 3:2)), BPO is used as an initiator (content is 1.2%), and polyvinyl alcohol is used as a dispersing agent (content is 0.2%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 180 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 49m 3 The oil absorption rate per gram can reach 19g/g.
Example 4
Styrene and divinylbenzene are used as monomers (DVB dosage is 24.3%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/ethyl acetate: 3:1)), BPO is used as an initiator (content is 1.2%), and polyvinyl alcohol is used as a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 180 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 18m 3 The oil absorption rate per gram can reach 12g/g.
Example 5
Styrene and divinylbenzene are used as monomers (DVB dosage is 24.3%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/ethyl acetate: 3:2)), BPO is used as an initiator (content is 3%), and polyvinyl alcohol is used as a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 200 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 72m 3 The oil absorption rate per gram can reach 22g/g.
EXAMPLE 6
Styrene and divinylbenzene are used as monomers (DVB dosage is 33.2%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/ethyl acetate: 3:2)), BPO is used as an initiator (content is 3%), and polyvinyl alcohol is used as a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 120 r/min. The prepared resin has a nano-pore structure and a specific surface area of 54m 3 The oil absorption rate per gram can reach 19.7g/g.
Comparative example 1
Styrene and divinylbenzene are used as monomers (DVB dosage is 14.3 percent), and the mixture is dissolvedThe agent is a pore-forming agent (total dosage 90% (paraffin/toluene: 1:3)), the BPO is an initiator (content 1.2%), the polyvinyl alcohol is a dispersing agent (content 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 180 r/min. The prepared resin has a nano-pore structure and a specific surface area of 0.1m 3 The oil absorption rate per gram can reach 2.3g/g.
Comparative example 2
Styrene and divinylbenzene are used as monomers (DVB dosage is 14.3%), a mixed solvent is used as a pore-forming agent (total dosage is 90% (paraffin/ethyl acetate: 1:2)), BPO is used as an initiator (content is 1.2%), and polyvinyl alcohol is used as a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 180 r/min.
The prepared resin has a nano-pore structure and a specific surface area of 0.5m 3 The oil absorption rate per gram can reach 4.1g/g.
Comparative example 3
Styrene and divinylbenzene are used as monomers (DVB dosage is 14.3%), a mixed solvent is a pore-forming agent (total dosage is 90% (paraffin/toluene: 3:2)), BPO is an initiator (content is 1.2%), and polyvinyl alcohol is a dispersing agent (content is 0.14%). The macroporous crosslinked polystyrene microsphere is prepared by adopting a suspension copolymerization method. The stirring rotation speed is controlled to be about 100 r/min. The prepared resin has larger particle diameter, larger than 60 meshes and specific surface area of 10m 3 The oil absorption rate per gram can reach 8.7g/g.
As can be seen from examples and comparative examples, the porous polymer microsphere degreasing resin is prepared by adopting styrene and divinylbenzene as monomers, controlling the dosage of divinylbenzene, controlling the dosage of an initiator and a dispersing agent, adopting a mixed solvent of paraffin and other pore-forming agents as a pore-forming agent, controlling the paraffin ratio, and controlling the stirring rate to carry out suspension polymerization reaction, and has a nano-pore structure of 18m 3 /g～72m 3 The specific surface area per gram is large, the oil absorption rate is high, and the oil absorption rate of the finished product is 12 g/g-22 g/g. If the paraffin wax ratio in the pore-forming agent is not in the range of the invention, or the stirring rate is not in the range of the invention, the technical effect of the invention cannot be achieved.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.

Claims (4)

1. The preparation method of the porous polymer microsphere degreasing resin is characterized by comprising the steps of mixing and adding a monomer, an initiator and a pore-forming agent into a dispersing agent solution for suspension polymerization reaction to prepare the porous polymer microsphere degreasing resin; wherein the monomers are styrene and divinylbenzene; the pore-forming agent is formed by mixing at least two of liquid paraffin, ethyl acetate, isobutyl acetate, toluene and silicone oil, and at least comprises the liquid paraffin, wherein the liquid paraffin accounts for 40% -80% of the pore-forming agent; the dosage of the pore-forming agent is 80-90 wt% of the dosage of the monomer; the dispersing agent is polyvinyl alcohol, and the dosage is 0.05wt.% to 0.2wt.% of the dosage of the monomer; the amount of the initiator is 1.2 to 4wt.% of the amount of the monomer; comprising the following steps:
s10, dissolving a dispersing agent by deionized water to obtain a dispersing agent solution; mixing and stirring an initiator, a monomer and a pore-forming agent to obtain a mixed solution;
step S20, adding the mixed solution into the dispersing agent solution, stirring for 30-1 h, wherein the stirring speed is 120-250 r/min, carrying out suspension polymerization at 60-85 ℃ for 1-2 h, and preserving heat at 90-100 ℃ for 2.5-5 h;
step S30, filtering the solution while the solution is hot, washing the solution with hot water at 60-80 ℃, wherein the consumption of the hot water is 3-5 times of the solution amount, and drying the solution at 80-110 ℃ for 22-2 hours to obtain granular particle resin; introducing phenolic hydroxyl groups into the granular particle resin for repolymerization to obtain high-adsorption resin, wherein the reaction temperature is 65-80 ℃ during repolymerization, and the reaction time is 3-6 h; the phenolic hydroxyl group-containing substance is phenol, phloroglucinol, resorcinol, vegetable tannin or urushiol, and the dosage is 0.3wt.% to 5wt.% of the dosage of the monomer;
and S40, cleaning the high adsorption resin by using toluene or acetone, and drying for 22-26 hours to obtain the porous polymer microsphere degreasing resin.
2. The method for preparing the porous polymeric microsphere degreasing resin according to claim 1, wherein the amount of divinylbenzene in the monomer is 14.3% -33.2%.
3. The method for preparing the porous polymeric microsphere degreasing resin according to claim 1, wherein the initiator is one or two of benzoyl peroxide, azobisisobutyronitrile and lauroyl peroxide.
4. The method for preparing the porous polymeric microsphere degreasing resin according to claim 1, wherein the porous polymeric microsphere degreasing resin has a nano-pore structure with a specific surface area of 18m 3 /g～72m 3 And/g, the oil absorption rate of the finished product is 12 g/g-22 g/g.
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